Lubricants



, .rosion and/or rusting of metal surfaces.

Patented Sept. 7, 1954 LUBRICANTS Morton Fainman, Chicago, Ill.,assignor to Standard Oil Company, Chicago, 111., a corporation ofIndiana No Drawing. Application November 23, 1949,

Serial No. 129,170

7 Claims. i

This invention is directed to improvements in oleaginous compositionsand more particularly relates to stable, corrosion and/ or rustinhibiting hydrocarbon oil compositions.

Organic substances such as normally nongaseous hydrocarbon products,particularly petroleum products, such as lubricating oils, turbine oils,insulating oils, greases, waxes and nonviscous petroleum products, suchas naphthas, gasolines, fuel oils, as well as synthetic hydrocarbonoils, are susceptible to oxidative deterioration. This oxidation takesplace under prolonged storage at atmospheric temperatures, as Well asduring use under elevated temperatures. Oxidative deterioration of thistype is also encountered with fats and fatty materials, such as animal,vegetable and marine oils, for example, cottonseed oil, corn oil, lardoil, tallow, menhaden oil, etc.

In many types of machinery and industrial equipment in which Water orsteam or other aqueous liquids are used which may become contaminatedwith such aqueous media, rusting and/ or corrosion of the metal. partsis encountered although oil may come in contact with such metal parts.For example, in internal combustion engines, water due to condensationaccumulates and causes rusting and/or corrosion of the ferrous metalparts of such engines. In the operation of steam turbines, rusting orcorrosion of the ferrous metal parts of such systems is also a seriousproblem and the prevention or inhibition of such rusting and/orcorrosion is highly important. Corrosion is also a serious problem inthe operation of textile machinery, in shock absorbers, in hydraulilifts, etc. Although equipment of the foregoing type usually employ anoil of some sort, the oil film which may form on the metal surfaces doesnot provide adequate protection against rusting and/or corrosion by theaqueous media due to the partial displacement of this oil film from themetal surfaces.

It is an object of the present invention to provide organic compositionswhich are resistant to oxidative deterioration and which prevent cor-Another object of the invention is to provide a composition containingan oleaginous material which is resistant to oxidative deterioration andwhich will prevent the rusting and/or corrosion of metal surfaces withwhich it comes in contact. A further object of the present invention isto provide compositions containing petroleum products which areresistant to oxidative deterioration and which are also effective inpreventing rusting and/or iii v or different alkyl radicals.

corrosion of metal surfaces coated with a film of said petroleumcomposition. Still another object of the invention is to provide apetroleum oil composition which is resistant to deterioration due tooxidation and which is capable of preventing rusting and/or corrosion ofmetal surfaces in contact with such petroleum oil compositions. Otherobjects and advantages will become apparent from the followingdescription thereof.

I have discovered that the foregoing objects can be attained byincorporating in organic compositions of the type hereinafter described,particularly petroleum products, such as petroleum oils, a small amount,sufficient to inhibit oxidative deterioration and to inhibit rustingand/or corrosion, of an oil-soluble ammonium salt of an arylol acidether obtained by reacting equimolar proportion of an amine and anarylol acid ether at a temperature of from about 50 F. to about 300 F.,and preferably from about 150 F. to about 250 F. The amine used ispreferably an amino compound known to possess antioxidant properties,particularly the aromatic amino compounds, such as for example, p-aminophenylbeta-naphthylamine, N-phenyl-p-phenylene diamine, p-aminoacetinalide, o-phenylene diamine, m-phenylene diamine, p-phenylenediamine, benzidine, p,pdiamino diphenyl methane, etc., and alkylenediamines, such as for example, 1-2 diamino ethane, 1-2 diamino butylethane, propylene polyamine, ethylene diamine, etc.

The arylol acid ether is preferably one having the general formulawherein R and R are substituents selected from the group consisting ofhydrogen or an alkyl group, A is a substituent selected from the groupconsisting of hydrogen or the group wherein R and R are as above, R" isa substituent selected from the group consisting of hydrogen, aryl,alkyl, aralkyl, alkaryl, and mixtures thereof, and n i an integer offrom 1 to 4, inclusive, and wherein R plus R contains 10 to 30 carbonatoms. R, R and B may be the same In the above formula 3 the ringstructure represents a monoor polynuclear aryl nucleus, such as phenyl,naphthyl,

etc. groups.

The preferred compounds are those in which A is hydrogen and n is 1 or2.

Representative of specific examples of compounds coming within the abovegeneral formula are the following:

Catechol mono-alpha-stearic acid ether 4 100 F. of about 100 seconds to350 seconds are employed. With the advent of drastic refining treatmentsto produce more highly refined turbine oils having improved color, etc.,desirable components for preventing the oxidative deterioration of theoils and these responsible for the wetting and therefore rust inhibitingqualities of the oil are removed. To overcome the susceptibility of suchoils to oxidative deterioration and to impart rust inhibiting propertiesthereto, small 2222: 351 i 'gggfi i i fig ggi 32 ther amounts, of theorder above stated, of the reac- Hydroquinone m l a1pha stgari c i ethertion product of an amine and an arylol acid ether I-Iydroquinonedi-alpha-stearic acid ether fi g g'fi g? igg g 2 13::Naphthalene-1,5-di-alpha-stearic acid ether 1 .g e i 0Y1 n hichPhloroglucinol mono-alpha-stearic acid ether W 2, ,1 o a WPhloroglucinol di-alpha-stearic acid ether i 1. i m {b1 fi mgfior 5 3Phloroglucinol tri-alpha-stearic acid ether 011 g fi g f g Catecholmono-alpha-lauric acid ether g o gmversa vlscos a 0 1 Resorcinol lauricstearic acid ether of 6 sewn. S gl 8 Hydroqu-mone dimalmitic acid etherof various ammonium sa ts of e presen inven- Catechol monmamhwoleic acidether 1310B. and subjected the followmg oxidat on Resorcinolmonmmontanic acid ether test. The oil composition 1s heated and mainphll i monmbahenic acid ether tamed at a temperature of about 100 F. whileC t monmlinoleic acid ether 2r blowing oxygen therethrough, and atstated pe- Pyrogallol mono-stearic acid the 0 riods a sample of the oilis withdrawn to determine the neutralization number thereof and the Theammonium salts of arylol acid ethers are test continued for 336 hours oruntil a sample eemphfied by the j g compounds has a neutralizationnumber of 2. The neu- Dl-bu yl-p-ph n l n xy tralization number isdetermined by adding two oxy-alpha-stearate grams of the sample to aneutral solution of 200 Para-ammo PhenylB'naphthylammomum'9'1- cubiccentimeters of naphtha and 100 cubic cenpha-alpha-dihydroxy-p fystealate timeters of 95% ethyl alcohol containing phenol-Phenyl-alpha-naphthylammomum-alphapara phthalein. The mixture is thentitrated with dlhydrexyphenoxy Steamte N/10 sodium hydroxide to thefirst pink color. l'z'dlammo ethane ortho dlhydmxyphenoxy Theneutralization number is calculated from the at??? d t h d h b equation:

y e e iamme symr1 y roxyp eno ehenate Xy c. c. NaOH norma1ity 56.1

Neutralization No. Para-ammo-acetamhde alpha ortho dihy- 40 Welght ofSample droxy-phenoxylaurate Butylethanolammonium-2-hydroxy-phenoxyal-The data obtained in the foregoing test are pha-stearate, etc. tabulatedin Table I.

TABLE I Oxidation test Time Until Neu- Appearance of Sample No.tralization No. of Sample After Sample Equals 2 Test Hours 1-Control (noadditive) 8 Red-brown sludge. 2Control+.l% 2-hydroxy phenoxy- 20 Nosludge.

alpha-stearic acid. 3Contr0l+.1% di-butyl-p-phenylene 160 D0.

di-amlne-2-hydroxy-phenoxy-alphastearate. 4Control+.l% P-aminophenyl-fi- 336 Do.

naphthylammonium-2-hydroxy phenoxy-alpna-stearate. 5Contro1+.l%Phenyl-alpha-naph- 320 Do.

thyl ammonium 2 hydroxy phen oxy-alpha-stearate.

It is not intended to imply that all amine salts of arylol acid ethersserve with identical efficiency; while they are all effective, they willexhibit some variation depending upon the nature and severity of theservice to which they are subjected. In general, it will be found. thatfrom about 0.0005% to about 2.0%, and preferably from about 0.003% toabout 0.5% by weight of the ammonium salt of arylol acid ether willprovide adequate protection.

For the purpose of illustrating the present invention the same will bedescribed as applied to steam turbine lubrication for which highly re-The effectiveness of these additives in inhibiting rusting isdemonstrated by the results obtained in the A. S. T. M. test for rustprevention, having the designation D665-47T. In this test 300 cc. of theoil to be tested are placed in a 400 cc. lipless glass beaker and heatedto 140 F. in an oil bath and the oil sample agitated with a stirrermaintained at about 1000 R. P. M. When the temperature of the oil samplereaches 140 F., a cleaned test strip of cold rolled steel is suspendedin the oil and the stirring continued for thirty minutes to insurecomplete wetting of the steel specimen. Thirty cc. of distilled waterare then carefully added to the beaker and the stirfined oils havingSaybolt Universal viscosities at ring continued for 48 hours. At the endof this time the steel specimen is removed from the beaker, washed withnaphtha and visually inspected for the presence of rust. Samples of aturbine oil base, namely a hydrocarbon oil having a Saybolt Universalviscosity at 100 F. of about 150 seconds containing small amounts ofvarious salts of the type herein described were subjected to this testand the results obtained tabulated in Table II.

The above data demonstrate the effectiveness of very small amounts ofthe additives in the present invention in inhibiting rusting.

Compositions containing the herein described ammonium salts of arylolacid ether can also contain in addition pourpoint depressors, extremepressure agents, viscosity improvers, detergents, etc.

While I have described my invention by reference to a specificembodiment thereof, the invention is not limited thereto, but includeswithin its scope such modifications and variations as come within thespirit of the appended claims.

I claim:

1. A composition comprising essentially a major proportion of an oil andan oil-soluble aromatic amino salt obtained by reacting an arylolcarboxylic acid ether with an aromatic amino compound selected from theclass consisting of a naphthylamine, a phenylenediamine and pp diaminodiphenyl methane, said salt being used in small but sufiicient amountsto inhibit the oxidative deterioration of said oil and to impart acorrosion-inhibiting property to said oil.

2. A composition as described in claim 1 in which the arylol carboxylicacid ether has the general formula 0 OH u 6 wherein R and R aresubstituents selected from the group consisting of hydrogen and an alkylgroup, A is a substituent selected from the group consisting of hydrogenand the group R 8-H JOOH in which R and R. are as above described, R isa substituent selected from the group consisting of hydrogen, aryl,alkyl, aralkyl, alkaryl radicals, and mixtures thereof, 11. is aninteger of from 1 to 4, inclusive and wherein R plus R contain fromabout 10 to about 30 carbon atoms.

3. A composition comprising essentially a normally non-gaseous petroleumfraction and from about 0.0005% to about 2.0% of an oil-soluble aromaticamino salt obtained by reacting an arylol carboxylic acid ether with anaromatic amino compound selected from the class consisting of anaphthylamine, a phenylenediamine and a pp diamino diphenyl methane.

4. A composition as described in claim 3 in which the arylol carboxylicacid ether is an arylol stearic acid ether.

5. A composition comprising essentially a hydrocarbon oil and from about0.0005% to about 2.0% ofdi-butyl-para-phenylenediamine-2-hydroxy-phenoxy-alpha-stearate.

6. A composition comprising essentially a hydrocarbon oil and from about0.0005% to about 2.0% of para-aminophenyl-beta-naphthylammonium-2-hydroxy-phenoxy-alpha-stearate.

7. A composition comprising essentially a hydrocarbon oil and from about0.0005% to about 2.0% of phenyl-alpha-naphthylammonium-2-hydroxy-phenoxy-alpha-stearate.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,198,293 Reiff et al. Apr. 23, 1940 2,252,665 'Reiff et a1.Aug. 12, 1941 2,426,496 Farley Aug. 26, 1947 2,447,483 Baker Aug. 24,-1948 2,459,717 Perry Jan. 18, 1949 2,470,276 Watkins May 17, 1949 OTHERREFERENCES Lubricating Oil Additives, by Kalichevsky, in PetroleumRefiner, vol. 28, No. 10, pages 127 and 128.

Polar Type Rust Inhibitors, I. and E. Chem., vol. 40, No. 12, pages 2338to 2347, page 2343 pertinent.

1. A COMPOSITION COMPRISING ESSENTIALLY A MAJOR PROPORTION OF AN OIL ANDAN OIL-SOLUBLE AROMATIC AMINO SALT OBTAINED BY REACTING AN ARYLOLCARBOXYLIC ACID ETHER WITH AN AROMATIC AMINO COMPOUND SELECTED FROM THECLASS CONSISTING OF A NAPHHYLAMINE, A PHENYLENEDIAMINE AND PP'' DIAMINODIPHENYL METHANE, SAID SALT BEING USED IN SMALL BUT SUFFICIENT AMOUNTSTO INHIBIT THE OXIDATIVE DETERIORATION OF SAID OIL AND TO IMPART ACORROSION-INHIBITING PROPERTY TO SAID OIL.